Ethylenically unsaturated oligomers and polymers resulting from the reaction of polyepoxides and unsaturated monocarboxylic acids have found widespread use in compositions and coatings that can be crosslinked to reduce the solubility and improve the chemical resistance of a cured product. In some instances where resistance to air inhibition of the crosslinking reaction has been desired, polyacrylic group-containing components have been introduced into the oligomers and polymers. In other instances where aqueous developability of coatings and films has been desired, carboxylic acid groups have been introduced into the oligomers and polymers.
In U.S. Pat. No. 3,367,992, there is disclosed thermosetting resins useful in laminates and the like. These resins are the reaction product of a hydroxyalkyl acrylate and a dicarboxylic acid anhydride. The partial ester obtained or its reaction product with a lower alkylene oxide may be reacted with polyfunctional reactants such as polyepoxides, polyisocyanates, polyamines and the like. Although products of the reaction of the partial ester of hydroxyalkyl acrylate and cyclic dicarboxylic acid anhydride with polyepoxides are described, the products do not contain polyacrylic group-containing components and carboxylic acid groups.
There are described in U.S. Pat. No. 3,448,089 copolymers suitable for coatings and printing plates containing a plurality of pendent acrylic ester groups and carboxylic acid groups. These copolymers, although being aqueous solution developable, do not contain poly(ethylenically unsaturated) group-containing components.
Curable compositions are described in U.S. Pat. No. 3,634,542 which contain the half ester prepared by reacting a polyepoxide with an ethylenically unsaturated organic monocarboxylic acid to form a hydroxy-substituted ethylenically unsaturated polyester that is then reacted with a dicarboxylic acid anhydride to esterify 5 to 100% of the hydroxyl groups. Such a reaction product, although developable with aqueous solutions, does not contain poly(ethylenically unsaturated) group-containing components.
In U.S. Pat. No. 3,980,483 there is described the free carboxylic group-containing esterification product of the addition compound of an epoxy resin and an .alpha., .beta.-unsaturated carboxylic acid with a dibasic carboxylic acid anhydride. Such a reaction product, although having free carboxylic acid groups and being therefore aqueous developable, does not contain poly(ethylenically unsaturated) group-containing components.
In U.S. Pat. No. 4,162,274 there is described a urethane resin suitable for resists and printing plates that is the reaction product of a polyepoxide and 60 to 100 mole percent of acrylic or methacrylic acid followed by reaction of 30 to 90 percent of the 2-hydroxyls formed with an isocyanate and 10 to 70% of the 2-hydroxyls with a dicarboxylic acid anhydride. Such a reaction product, although having free carboxylic acid groups and being therefore aqueous developable, does not contain poly(ethylenically) unsaturated group-containing components.
In U.S. Pat. No. 4,187,257 there is disclosed radiation crosslinkable resins that are the reaction product of a polyepoxide and a monoester of a dicarboxylic acid and a di- or tri-acrylate of pentaerythritol. It is stated at Col. 5 lines 30-36 that, "The resins of this invention are further modified by known procedures prior to curing. Thus, the secondary hydroxyls resulting from esterification of an oxirane group may be reacted with a Group II metal oxide or hydroxide to provide thickened resins useful in sheet molding compound and bulk molding compound. Other modifications will be apparent." The reaction products described in this patent, although containing poly(ethylenically unsaturated) group-containing components, do not contain carboxylic acid groups and therefore would not be aqueous developable.
In U.S. Pat. No. 4,228,232 (3M) there is disclosed a urethane oligomer useful in recording elements that is the reaction product of a polyester polyol or polyether polyol having p+q hydroxyl groups (p is 2 to 7.7 and q is 0.3 to 4) with p moles of the 1:1 reaction product of a hydroxyalkyl acrylate or methacrylate and a polyisocyanate followed by the reaction with q moles of dicarboxylic acid anhydride. Such a reaction product, although having free carboxylic acid groups and being therefore aqueous developable, does not contain poly(ethylenically unsaturated) group containing components.
U.S. Pat. No. 4,249,011 discloses radiation curable oxygen insensitive systems that contain poly(ethylenically unsaturated alkoxyalkyl)heterocyclic compounds. These compounds are the reaction products of a poly(ethylenically unsaturated) primary alcohol and an poly epoxy-substituted heterocycle that can be acylated by various acylating agents, e.g., isocyanates including acryloyloxyethyl isocyanate, and dicarboxylic acid anhydrides such as succinic anhydride.
Japanese Patent No. 60-121444 (6/28/85) (abstract) describes a resin useful in photoresists and the like having high definition and good durability that is the reaction product of (1) a chain polymer having carboxyl, amino, thio, isocyanate or hydroxyl groups and having a number average molecular weight of 500 to 20,000; (2) two or more aromatic or alicyclic polyepoxide compounds; (3) an unsaturated compound having a group reactive with an epoxide group or a hydroxyl group, and (4) an acid anhydride or a compound having carboxyl or phenolic hydroxyl groups and one or more groups reactive with the functional groups in (1) or (2).
While materials are described in the above cited references which can provide compositions that on coated articles are rapidly crosslinked, insensitive to air inhibition, and aqueous developable, there is still need for improved materials that have still faster curing, are aqueous developable, have a low volatility, and have simplicity of preparation.